EP1367068A1 - Polymères de propylène - Google Patents

Polymères de propylène Download PDF

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Publication number
EP1367068A1
EP1367068A1 EP02011675A EP02011675A EP1367068A1 EP 1367068 A1 EP1367068 A1 EP 1367068A1 EP 02011675 A EP02011675 A EP 02011675A EP 02011675 A EP02011675 A EP 02011675A EP 1367068 A1 EP1367068 A1 EP 1367068A1
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EP
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Prior art keywords
polymer
mfr
propylene polymer
weight
propylene
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EP02011675A
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German (de)
English (en)
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EP1367068B1 (fr
Inventor
Toshihiko Sugano
Masaaki Ito
Kiyoshi Yukawa
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Japan Polypropylene Corp
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Japan Polychem Corp
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Priority to US10/145,737 priority Critical patent/US6756463B2/en
Application filed by Japan Polychem Corp filed Critical Japan Polychem Corp
Priority to AT02011675T priority patent/ATE361325T1/de
Priority to DE2002619891 priority patent/DE60219891T2/de
Priority to EP02011675A priority patent/EP1367068B1/fr
Publication of EP1367068A1 publication Critical patent/EP1367068A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

Definitions

  • This invention relates to propylene polymers which are excellent in rigidity and heat resistance and have an appropriate melt tension and favorable molding processability and appearance.
  • propylene polymers Because of having the characteristics of being excellent in rigidity, heat resistance, molding properties, transparency and chemical resistance, propylene polymers have attracted public attention and are widely used for a number of purposes such as various industrial materials, various containers, daily necessities, films and fibers.
  • Metallocene catalysts with the use of metallocene transition metal compounds have been widely employed in their production, since these catalysts generally have a high activity and propylene polymers obtained thereby are excellent in stereostructural properties.
  • the propylene polymers produced by using metallocene catalysts have a disadvantage of having a small memory effect (ME) due to a narrow molecular weight distribution and thus showing a poor molding processability.
  • ME is a value serving as an indication of the non-Newtonian properties of a resin.
  • a higher ME indicates the wider molecular weight distribution and a tendency towards more favorable molding properties particularly owing to the effects of high-molecular weight components.
  • 2001-500176 proposes to broaden molecular weight distribution by using two types of Zr complexes having high stereoregularity.
  • the distribution is about 7 or lower
  • ME cannot be improved by these methods.
  • ME can be improved thereby in a system having a larger molecular weight distribution value, no homogeneous mixture can be obtained, which results in a tendency that the molding appearance is worsened. It is therefore required to solve these problems.
  • Japanese Patent Laid-Open No. 181343/2001 and No. 294609/2001 propose polymers having Mw/Mn ratios ranging from 6 to 50 and a process for producing the same. Although these polymers have high Mw/Mn ratios, MEs thereof are not so high.
  • Japanese Patent Laid-Open No. 288220/2001 proposes single-peak polymers having Mw/Mn values of from 4 to 6.
  • Mw/Mn values of from 4 to 6.
  • the present invention provides propylene polymers which are not only excellent in rigidity and heat resistance but also contain an appropriate amount of high-molecular weight components with little eluting components and have excellent molding processability.
  • the propylene polymer of the present invention which may be copolymerized with ethylene of 0 to 7% by weight, is characterized by comprising satisfying the following requirements:
  • the present invention is also characterized in that the propylene polymer has been polymerized by using a metallocene catalyst.
  • the present invention provides novel propylene polymers meeting with the physiological requirements (1) to (5) as described below.
  • the propylene polymer according to the present invention has a melt flow rate (MFR) measured at 230°C under a 2.16 kg load of from 0.1 to 1000 g/10 min. It is unfavorable from the viewpoint of the molding process that MFR is lower than 0.1, since the fluidity of the polymer is extremely worsened in this case. It is also unfavorable that MFR exceeds 1000, since the impact strength of the polymer is extremely lowered in this case.
  • MFR melt flow rate
  • the MFR ranges from 0.5 to 500.
  • Favorable uses are restricted depending on the MFR level. In the case of applications in injection molding, it is favorable that MFR ranges from 10 to 300. In the case of applications in film-molding or sheet-molding, it is favorable that MFR ranges from 0.5 to 10, still preferably from 1.0 to 10.
  • the propylene polymer according to the present invention has an isotactic triad fraction measured by 13 C-NMR in the propylene unit chain moiety made up of head-to-tail bonds (i.e., the ratio of propylene unit triads, in which propylene units are bonded to each other via head-to-tail bonds and the methyl branches in the propylene units are in the same direction, to arbitrary propylene unit triads in the polymer chain) of 99.0% or above, preferably 99.5% or above.
  • the isotactic triad fraction will be sometimes referred to as mm fraction thereinafter.
  • This isotactic triad fraction is a value which indicates that the stereostructure of methyl groups in the polypropylene molecular chain is isotactically regular.
  • a higher value means a higher extent of the regularity. In case where this value is less than the lower limit as specified above, there arises a problem of poor heat resistance.
  • the 13 C-NMR spectrum can be measured by the following method. Namely, the 13 C-NMR spectrum is measured by completely dissolving a sample (350 to 500 mg) in a solvent prepared by adding about 0.5ml of deuterated benzene which is a lock solvent to about 2.0 ml of o-dichlorobenzene in an NMR sample tube of 10 mm in diameter followed by the measurement by the proton complete decoupling method at 130°C.
  • the measurement conditions are selected so as to give a flip angle of 65° and a pulse interval of 5T 1 or longer (wherein T 1 stands for the maximum value in the methyl group spin-lattice relaxation times).
  • T 1 of methylene group and T 1 of methine group are shorter than T 1 of methyl group.
  • the recovery ratios of the magnetization of all carbon atoms become 99% or above under these measurement conditions.
  • NMR peaks of the propylene polymer of the present invention are identified in accordance with a publicly known method described in Japanese Patent Laid-Open No. 273507/1998.
  • the methyl group in the third unit of a propylene unit pentad in which the chemical shift is bonded via a head-to-tail bond and the methyl branches are in the same direction, is referred to as 21.8 ppm and chemical shifts of other carbon peaks are determined on the basis of this standard.
  • the peak assignable to the methyl group in the second unit of the propylene triad represented by PPP [mm] appears within the range of 21.3 to 22.2 ppm
  • the peak assignable to the methyl group in the second unit of the propylene triad represented by PPP [mr] appears within the range of 20.5 to 21.3 ppm
  • the peak assignable to the methyl group in the second unit of the propylene triad represented by PPP [rr] appears within the range of 19.7 to 20.5 ppm.
  • the Q value i.e., the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) measured by gel permeation chromatography (GPC) is specified as ranging from 2.0 to 6.0. It is unfavorable from the viewpoint of operation that the Q value.is lower than 2.0, since the resin pressure is elevated in the process of molding the polymer in this case. It is also unfavorable that the Q value exceeds 6.0, since the molecular distribution shifts toward the low-molecular weight side too and thus low-molecular weight components are increased, thereby worsening the physical properties such as rigidity in this case.
  • the polymer according to the present invention is characterized by essentially containing little low-molecular weight components and CXS components. It is preferable that the Q value ranges from 2.5 to 5.5, still preferably from 3.0 to 5.0.
  • the propylene polymer according to the present invention is characterized in that the correlation between memory effect (ME), which serves as an indication of the content of high-molecular weight components in the polymer, and MFR, which serves as an indication of the average molecular weight of the polymer, is in a specific relationship represented by the following formula (I).
  • ME is an indication relating to the molding properties and surface appearance of a polymer and generally correlates to the molecular weight and molecular weight distribution.
  • the optimum range of ME varies depending on purpose. In the case of films, sheets and injection molding, an excessively small ME generally results in an increase in the resin pressure during molding and thus there arise some problems such as uneven film thickness or flow irregularities in injection molding.
  • the polymer according to the present invention has a correlationship between ME and MFR within a specific range while maintaining the molecular weight distribution as described above 1.75 ⁇ (ME) + 0.26 x log(MFR) ⁇ 1.40
  • the polymer according to the present invention is characterized by having a relatively large ME with respect to MFR compared with conventionally known uniform polymers. It is known that an appropriately high ME contributes to the achievement of favorable molding properties. Thus, the propylene polymer according to the present invention is excellent in molding properties. It is still preferable that the relationship represented by the following formula (I-1) is satisfied. 1.75 ⁇ (ME) + 0.26 x log (MFR) ⁇ 1.45 It is further preferable that the relationship represented by the following formula (I-2) is satisfied. 1.75 ⁇ (ME) + 0.26 x log(MFR) ⁇ 1.55
  • the propylene polymer may be a copolymer.
  • the (co)polymer according to the present invention is characterized in that the cold xylene solubles (CXS) at 23°C, which indicates the low-crystallinity components in the polymer, MFR, which indicates of the polymer molecular weight, and the ethylene unit content [C2] (unit: % by weight), which indicates the polymer crystallinity, satisfy the relationship represented by the following formula (II).
  • [C2] in the following formula is 0. It is known by experience that CXS primarily correlates to MFR and ethylene content.
  • a polymer having a smaller molecular weight i.e., a larger MFR
  • MFR molecular weight
  • the crystallinity of the polymer is lowered and thus the polymer becomes more soluble in water, thereby causing a decrease in the CXS value.
  • the content of the ethylene comonomer is from 0 to 7% by weight, preferably from 0 to 5% by weight. It is preferable that the polymer is a homopolymer.
  • the polymer according to the present invention is characterized by having little CXS. Namely, it contains little low-crystallinity components and low-molecular weight components causing a high stickiness of products, worsening rigidity or heat resistance, etc.
  • the polymer satisfies the relationship represented by the following formula (II-2).
  • CXS ⁇ 0.5 x [C2] + 0.2 x log(MFR) + 0.3
  • the propylene polymer according to the present invention is preferably characterized by having a melting temperature Tm (°C) measured by DSC of 120°C or above.
  • Tm melting temperature measured by DSC
  • the melting temperature can be elevated by reducing the amount of a comonomer to be used in the polymerization and thus lowering the ethylene content in the polymer.
  • a propylene-ethylene random copolymer containing about 5 to 6% by weight of ethylene has a melting temperature of about 120 to 130°C.
  • the propylene homopolymer according to the present invention has a polymer melting temperature (Tmh) of 149°C or above, still preferably 155°C or above and particularly preferably 157°C or above.
  • Tmh polymer melting temperature
  • the melting temperature (Tmr) of the random copolymer preferably satisfies Tmr ⁇ 120°C and the relationship Tmr ⁇ 149-5.5 [E] wherein [E] represents the content (% by weight) of ethylene in the polymer, more preferably Tmr ⁇ 155-5.5 [E], and particularly preferably Tmr ⁇ 157-5.5 [E].
  • the propylene polymer according to the present invention may be prepared by an arbitrary process without restriction, so long as a propylene polymer satisfying the above requirements can be obtained thereby.
  • metallocene catalysts are adequate as a catalyst system to be used in producing the polymer of the present invention and it is preferable to use a specific metallocene catalyst.
  • the propylene polymer can be produced by using the following catalysts.
  • Component A at least one metallocene compound selected from the transition metal compounds as will be cited herein below;
  • component B at least one compound selected from the group consisting of ion-exchange layered silicates; optionally together with
  • component C an organic aluminum compound.
  • transition metal compounds to be used as the component A constituting polymerization catalysts which are favorable in producing the propylene polymer according to the present invention are transition metal compounds represented by the following general formula (1).
  • Q represents a linkage group cross linking two conjugated five-membered cyclic ligands
  • M represents a metal atom selected from among titanium zirconium and hafnium
  • X and Y represent each a hydrogen atom, a halogen atom, a hydrocarbyl group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbyl group, a phosphorus-containing hydrocarbyl group or a silicon-containing hydrocarbyl group bonded to M
  • R 1 and R 3 represent each hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a silicon-containing hydrocarbyl group, a nitrogen-containing hydrocarbyl group, an oxygen-containing hydrocarbyl group, a
  • Q represents a divalent linkage group crosslinking two conjugated five-membered cyclic ligands and examples thereof include:
  • an alkylene group and a silylene group having a hydrocarbyl group as a substituent are preferable.
  • X and Y may be either the same or different and each independently represents the following preferred groups: (a) hydrogen , (b) a halogen, (c) a hydrocarbyl group having 1 to 20, preferably 1 to 12, carbon atoms, or (d) a hydrocarbyl group having 1 to 20, preferably 1 to 12, carbon atoms and containing oxygen, nitrogen or silicon.
  • preferable examples thereof include hydrogen, chlorine, methyl, isobutyl, phenyl, dimethylamido and diethylamido groups, etc.
  • R 1 and R 3 represent each hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a silicon-containing hydrocarbyl group, a nitrogen-containing hydrocarbyl group, an oxygen-containing hydrocarbyl group, a boron-containing hydrocarbyl group or a phosphorus-containing hydrocarbyl group.
  • Specific examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl naphthyl, butenyl and butadienyl groups, etc.
  • hydrocarbyl groups In addition to the hydrocarbyl groups, citation may be made, as typical examples thereof, of methoxy, ethoxy, phenoxy, trimethylsilyl, diethylamino, diphenylamino, pyrazolyl, indolyl, dimethylphosphino, diphenylphosphino, diphenylboron and diemthoxyboron groups, etc. containing halogen, silicon, nitrogen, oxygen, boron, phosphorus, etc. Among them, hydrocarbyl groups are preferable and methyl, ethyl, propyl and butyl groups are particularly preferable.
  • R 2 represent each hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a silicon-containing hydrocarbyl group, a nitrogen-containing hydrocarbyl group, an oxygen-containing hydrocarbyl group, a boron-containing hydrocarbyl group or a phosphorus-containing hydrocarbyl group.
  • aryl groups having 6 to 16 carbon atoms more specifically, phenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, aceantrithrenyl groups, etc. are preferable,
  • aryl groups may be substituted by a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbyl group, an oxygen-containing hydrocarbyl group, a boron-containing hydrocarbyl group or a phosphorus-containing hydrocarbyl group.
  • a halogen a hydrocarbyl group having 1 to 20 carbon atoms
  • a halogenated hydrocarbyl group having 1 to 20 carbon atoms a nitrogen-containing hydrocarbyl group
  • an oxygen-containing hydrocarbyl group a boron-containing hydrocarbyl group or a phosphorus-containing hydrocarbyl group.
  • phenyl and naphthyl groups are preferable.
  • M is a metal selected from among titanium, zirconium and hafnium and hafnium is preferable.
  • Non-limiting examples of the above-described transition metal compounds are as follows:
  • particularly preferable compounds include dimethylsilylenebis(2-ethyl-4-(2-fluoro-4-biphenyl)-4H-azu lenyl)hafnium dichloride, dimethylsilylenebis(2-ethyl-4-(4-chloro-2-naphthyl-4H-azul enyl)hafnium dichloride and dimethylsilylenebis(2-ethyl-4-(3-chloro-4-t-butyl-4H-azule nyl))hafnium dichloride.
  • a polymer according to the present invention which is excellent in molding properties and contains less xylene solubles, is not a technique common to all metallocenes.
  • it is required to have a special structure capable of forming heterologous active sites differing in hydrogen-dependency in a state of being carried on a clay mineral.
  • Complexes having the azulene skeleton are liable to exert such characteristics. Even in azulene-type compounds, these characteristics can be hardly exhibited in case where the seven-membered ring is hydrogenated.
  • these characteristics closely relate to the state of carriers and the method of carrying as will be described hereinafter. It is therefore not essentially in the present invention to specify the structure of the complex. Accordingly, the above description merely indicates an example of the formation of the polymer according to the present invention.
  • At least one compound selected from the group consisting of ion-exchange layered silicates to be used as the component B in the present invention is a silicate compound having a crystalline structure in which planes formed by ionic bonds, etc. are piled up in parallel at weak bonding strength and the ion contained therein is exchangeable.
  • Most of ion-exchange layered silicates are produced as the main components of clay minerals in nature. However, these ion-exchange layered silicates are not restricted to natural ones but artificial ones are also usable.
  • ion-exchange layered silicate examples include publicly known layered silicates described in "Nendo Kobutugaku", Haruo Shiramizu, Asakura-shoten (1995), etc. It is preferable to use smectites, vermiculites and micas such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite or teaniolite.
  • the component B may be used as such without resort to any special treatment, it is preferable to chemically treat the component B.
  • the chemical treatment use may be made of either a surface treatment for eliminating impurities adhering to the surface or a treatment affecting the crystalline structure of the clay. More specifically, examples of the treatment include acid-treatments, alkali-treatment, salt-treatment and organic matter-treatments.
  • the salt to be used in the salt-treatment aiming at the ion exchange is a compound consisting of a cation containing at least one atom selected from the group consisting of the atoms of the groups 1 to 14 and at least one anion selected from the group consisting of halogen atoms, inorganic acids and organic acids.
  • it is a compound consisting of a cation containing at least one atom selected from the group consisting of the atoms of the groups 2 to 14 and at least one anion selected from the group consisting of Cl, Br, I, F, PO 4 , SO 4 , NO 3 , CO 3 , C 2 O 4, , ClO 4 , OOCCH 3 , CH 3 COCHCOCH 3 , OCl 2 , O(NC 3 ) 2 , O(ClO 4 ) 2 , O(SO 4 ), OH, O 2 Cl 2 , OCl 3 , OOCH, OOCCH 2 CH 3 , C 2 H 4 O a and C 3 H 5 O 7 .
  • the process for selecting the polymer according to the present invention varies depending on the complex, carrier and the method of using hydrogen during the polymerization. Therefore, it is not essential in the present invention to specify the method of treating the component (B).
  • the non-uniformity formation of heterologous active sites occurring in carrying the complex is caused by the formation of sites having different acidities on the clay surface. Owing to the balance between the extent of the non-uniformity and the degrees of the easiness in carrying the complex at the respective sites, a PP polymer having a special balance, which is never observed in the conventional polymers, can be produced.
  • impurities on the surface can be eliminated and, moreover, a part or all of cations such as Al, Fe or Mg in the crystalline structure can be eluted.
  • the acid to be used in the acid-treatment is selected from among hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
  • Two or more salts and acids may be used in the treatment.
  • the conditions for the salt- and acid-treatment are not particularly restricted, it is preferable that the treatment is performed at a salt and acid concentration of from 0.1 to 50% by weight and at a temperature from room temperature to the boiling point of the solvent for 5 minutes to 24 hours so that at least a part of the substance(s)constituting at least one compound selected from the group consisting of the ion-exchange layered silicates can be eluted.
  • the salts and acids are usually employed as an aqueous solution.
  • ion-exchange layered silicates usually contain adsorption water and interlayer water. It is preferable in the present invention to use such an ion-exchange layered silicate as the component B after removing these absorption water and interlayer water.
  • the heat treatment method for removing the adsorption water and the interlayer water is not particularly restricted, it is necessary to select such conditions as enabling the complete removal of the interlayer water without causing structural destruction.
  • the heating is performed for 0.5 hour or longer, preferably an hour or longer.
  • the moisture content of the component B after the treatment is 3% by weight or less, still preferably 1% by weight or less, where the moisture content achieved after dehydrating at a temperature of 200°C under a pressure of 1 mmHg for 2 hours is referred to as 0% by weight.
  • the component B an ion-exchange layered silicate having a moisture content of 3% by weight or less which is obtained by treatment with salts and/or acids.
  • spherical particles having an average particle diameter of 5 ⁇ m or above.
  • a natural substance or a marketed product may be used as such, so long as the particles are spherical.
  • use can be made of particles the shape and diameter of which have beencontrolledbygranulation, classification, fractionation, etc.
  • Examples of the granulation method to be used herein include stirring granulation and spray granulation. It is also possible to use a marketed product. In the granulation, use may be made of organic matters, inorganic solvents, inorganic salts or various binders.
  • the spherical particles thus obtained have a compressive destruction strength of 0.2 MPa or above, still preferably 0.5 MPa or above. In case where the particles have such a strength, the effect of improving the particle properties can be effectively achieved particularly in performing pre-polymerization.
  • Examples of the organic aluminum compound to be used as the component C in a preferable polymerization catalyst in the present invention include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum and halogen- or alkoxy-containing alkylammoniums such as diethylaluminum monochloride and diethylaluminum monomethoxide represented by the following general formula: AlR a P 3-a wherein R represents a hydrocarbyl group having 1 to 20 carbon atoms; P represents hydrogen, halogen or an alkoxy group; and a is an integer satisfying the requirement 0 ⁇ a ⁇ 3. It is also possible to use aluminoxanes such as methylaluminoxane. Among them, a trialkylaluminum is particularly preferable.
  • the component A, the component B and, if needed, the component C are brought into contact with each other to give a catalyst.
  • the contact may be carried out in the following orders, though the present invention is not restricted thereto.
  • the contact may be performed not only in the step of preparing the catalyst but also in the pre-polymerization of the olefin or in the polymerization of the olefin.
  • the three components may be brought into contact with each other at the same time.
  • a polymer such as polyethylene or polypropylene or an organic oxide such as silica or alumina may coexist or come into contact.
  • Contacting may be carried out in an inert gas or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene.
  • the contact temperature is from -20°C to the boiling point of the solvent, particularly preferably from room temperature to the boiling point of the solvent.
  • the catalyst thus obtained may be used as such without washing with an inert solvent.
  • a solvent in particular, a hydrocarbon such as hexane or heptane before use.
  • the above-described component C maybe newly combined therewith.
  • the amount of the component C employed herein is selected so as to give an atomic ratio of the aluminum in the component C to the transition metal in the component A of 1:0 to 1:10,000.
  • a catalyst prepared by pre-polymerizing an olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane or styrene followed by, if needed, washing.
  • an olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane or styrene followed by, if needed, washing.
  • prepolymerization it is preferable to carry out this prepolymerization in an inert solvent under mild conditions. It is desirable that the prepolymerization is performed so that from 0.01 to 1000 g, preferably from 0.1 to 100 g, of the polymer is formed per gram of the solid catalyst.
  • the polymerization reaction is carried out either in the presence or absence of an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene or cyclohexane or a solvent such a as liquefied ⁇ -olefin.
  • the polymerization temperature ranges from -50°C to 250°C, while the pressure preferably ranges from atmospheric pressure to about 2000 kg•f/cm 2 , though the present invention is not restricted thereto.
  • the polymerization can be performed either by the batch method, the continuous method or the semi-batch method.
  • the molecular weight and the molecular weight distribution can be controlled to give the desired polymer.
  • the Q value also depends on the polymerization temperature and the polymerization pressure, it can be regulated within a desired range by optimizing these factors.
  • a metallocene catalyst particularly vigorously consumes hydrogen, the-hydrogen concentration varies widely in case of feeding hydrogen exclusively in the early stage. In this case, a low-molecular weight polymer is formed in the early stage and then an ultrahigh-molecular weight polymer is formed in the later stage under hydrogen-free conditions.
  • a metallocene catalyst capable of forming an ultrahigh-molecular weight polymer under the hydrogen-free conditions problems might arise in that the ME becomes excessively large and thus worsens the molding properties or the appearance of molded articles. Accordingly, it is beneficial to regulate the hydrogen concentration within a specific range in the course of the polymerization. Therefore, it is preferable in the present invention to use a device by which hydrogen can be continuously fed so as to maintain the hydrogen concentration at a constant level throughout the polymerization.
  • hydrogen it is preferable to continuously feed hydrogen so as to maintain the hydrogen concentration in the gas phase in an autoclave at a constant level throughout the polymerization in case of bulk polymerization by the batch method or gas phase polymerization.
  • the hydrogen concentration may be regulated to an arbitrary level from 1 ppm to 10000 ppm.
  • the hydrogen concentration may be regulated to an arbitrary level from 1 ppm to 10000 ppm too.
  • Copolymerization may carried out by adding a small amount of an ⁇ -olefin (C 4 to C 6 ) other than ethylene, as long as the physical properties of the polymer disclosed in the present invention are not impaired thereby.
  • the ⁇ -olefin may be added in an amount up to 6.0% by mol based on propylene.
  • the physical properties are respectively defined by using the following measurement methods and apparatus.
  • a propylene polymer sample was blended with 0.10% by weight of IRGANOX1010 (manufactured by Ciba Speciality Chemicals), 0.10% by weight of IRGAFOS168 (manufactured by Ciba Speciality Chemicals) and 0.05% by weight of calcium stearate at blending ratio (% by weight) and kneaded and granulated in a monoaxial extruder to give a resin composition in the form of pellets.
  • the sample pellets thus obtained were subjected to the following measurements.
  • MFR unit: g/10 min
  • JIS-K7210 230°C, under 2.16 kg load
  • the weight-average molecular weight Mw and the number-average molecular weight Mn were measured by using Model GPC150C (manufactured by Waters), three AD80M/S columns (manufactured by Showa Denko) and o-dichlorobenzene as a solvent at a measurement temperature of 140°C.
  • Apparatus Melt Indexer manufactured by Takara. Measurement method: The sample was extruded at 190°C from orifices (diameter: 1.0 mm, length: 8.0mm) under loading. At an extrusion speed of 0.1 g/min, the polymer extruded from the orifices was quenched in methanol and then the strand diameter was calculated.
  • the ethylene unit content (unit: %by weight) inthepolymer originating in ethylene comonomer was determined by pressing the obtained polymer into a sheet and measuring by the IR method. More specifically, it was calculated from the height of a peak assignable tothemeihylene chain which was observed at around 730 cm -1 .
  • a sample (about 5 mg) was weighed, molten at 200°C for 5 minutes and then crystallized by cooling to 40°C at a rate of 10°C/min. Next, it was molten by heating to 200°C at a rate of 10°C/min. Then evaluation was made on the basis of the melting peak temperature and the temperature at the completion of melting.
  • 2-Bromo-4-chloronaphthalene (2.50 g, 10.30 mmol) was dissolved in a solvent mixture of diethyl ether (50 mL) and hexane (7.5 mL). Then a hexane solution of n-butyllithium (6.8 mL, 10.4 mmol, 1.53 N) was dropped thereinto at 19°C. After stirring at 20°C for 1 hour, 2-ethylazulene (1.47 g, 9.41 mmol) was added to this solution at 5°C followed by stirring at room temperature for 1 hour. In the course of the stirring, diethyl ether (5.0 mL) was added.
  • reaction product (3.09 g, 4.21 mmol) obtained above was dissolved in diethyl ether (44 mL). After dropping a hexane solution of n-butyllithium (5.5 mL, 8.41 mmol, 1.53 mol/L) at -70°C, the mixture was slowly heated and stirred at room temperature for 2 hours. After distilling off the solvent, toluene (11mL) and diethyl ether (99mL) wereadded. Themixture was cooled to -70°C and, after adding hafnium tetrachloride (1.375 g, 4.29 mmol), slowly heated and stirred at room temperature overnight.
  • a 500 mL round-bottomed flask was provided with a vacuum stirrer. Then 196.5 g of ion-exchanged water and 51.25 g (525 mmol) of sulfuric acid were successively added thereto followed by stirring. Further, 12.45 g (525 mmol) of lithium hydroxide was added and dissolved therein.
  • the liquid mixture of the montmorillonite slurry and the dimethylsilylenebis(2-ethyl-4-(4-chloro-2-naphthyl-4H-azulenyl)hafnium dichloride prepared above was fed into a stirring autoclave having an internal volume of 1.0 L which had been sufficiently purged with nitrogen. Further, heptane was added to give a total volume of 500 ml and the resultant mixture was maintained at 30°C.
  • the analytical data of this polymer were as follows: isotactic triad fraction: 99.5%; MFR: 11.30 g/10 min; weight-average molecular weight by GPC: 224500; Mw/Mn: 3.27; melting temperature: 158.5°C; CXS: 0.40% by weight; and ME: 1.36.
  • the analytical data of this polymer were as follows: isotactic triad fraction: 99.3%; MFR: 4.64 g/10 min; weight-average molecular weight by GPC: 303300; Mw/Mn: 3.69; melting temperature Tm: 157.5°C; CXS: 0.45% by weight; and ME: 1.49.
  • the analytical data of this polymer were as follows: isotactic triad fraction: 99.4%; MFR: 6.07 g/10 min; weight-average molecular weight by GPC: 255500; Mw/Mn: 3.17; melting temperature Tm: 149.2°C; ethylene content: 1.22% by weight; CXS: 0.50% by weight; and ME: 1.44.
  • a PP homopolymer (MA3UQ manufactured by Nippon Polychem) prepared by using the Ziegler-Natta catalyst was subjected to the same analysis and measurement of physical properties.
  • the analytical data of this polymer were as follows: isotactic triad fraction: 97.8%; MFR: 7.80 g/10 min; weight-average molecular weight by GPC: 310000; Q value: 4.5; melting temperature Tm: 164.0°C; CXS: 1.8% by weight; and ME: 1.33.
  • the mixture was heated to 65°C to thereby initiate polymerization and then maintained at this temperature for 3 hours. Then 100 ml of ethanol was injected to thereby cease the reaction. After purging the remaining gases, the polymer was dried. Thus, 7.0 kg of the polymer was obtained.
  • 2-Fluoro-4-bromobiphenyl (4.63 g, 18.5 mmol) was dissolved in a solvent mixture of diethyl ether (40 mL) and hexane (40 mL). Thenapentane solution of n-butyllithium (22.8 mL, 36.9 mmol, 1.62 N) was dropped thereinto at -78°C and the resultant mixture was stirred at -5°C for 2 hours.
  • the racemic/meso mixture (1.1 g) obtained above was suspended in dichloromethane (30 mL) and irradiated with a high-pressure mercury lamp (100W) for 30 minutes. Then the solution was distilled under reduced pressure. The solid thus obtained was suspended by adding dichloromethane (40 mL) and filtered. After washing with hexane (3 mL) and dried under reduced pressure, the racemic compound (577 mg, 52%) was obtained.
  • liquefied propylene, hydrogen and TIBA were continuously fed.
  • the liquefied propylene and TIBA were fed respectively at rates of 90 kg/h and 21.2 g/h, while hydrogen was fed to give amolar concentration [H 2 ] of 30 ppm.
  • the solid catalyst component (A) obtained above was fed thereinto so as to give a concentration of the solid component contained in (A) of 1.36 g/h.
  • the polymerization tank was cooled to thereby adjust the polymerization temperature to 65°C.
  • the slurry polymerized in this polymerization tank was withdrawn by using a slurry pump.
  • the slurry was withdrawn at such a rate as to give the concentration of the polypropylene particles contained in the slurry of about 10.8 kg/h.
  • the average residence time of the polypropylene particles in the liquid phase polymerization tank was 2 hours.
  • the average particle diameter (Dp50) of the polypropylene particles was 436 ⁇ m, the average CE thereof was 7900/g, the polymer MFR was 2.3 g/10 min, the CXS was 0.26% by weight, the Q value was 4.5 and the ME was 1.54.
  • the catalytic efficiency (CE) is defined as the yield (g) of polypropylene per gram of the solid component contained in the solid catalyst component (A).
  • Example 4 The procedure of Example 4 was followed but maintaining the hydrogen concentration [H 2 ] at 200 ppm, feeding 1.63 g of the catalyst and controlling the average residence time to 1.5 h.
  • the average particle diameter (Dp50) of the obtained polymer was 457, the average CE thereof was 10300/g, the polymer MFR was 63/10 min, the CXS was 0.20% by weight, the Q value was 4.0 and the ME was 1.23.
  • the analytical data of this polymer were as follows: isotactic triad fraction: 99.5%; MFR: 2.0 g/10 min; weight-average molecular weight by GPC: 358000; Mw/Mn: 4.39; melting temperature: 160.0°C; CXS: 1.30% by weight; and ME: 1.27.
  • Polymerization was carried out by feeding 7.0 NL of hydrogen at the early stage but feeding no more hydrogen thereafter.
  • 22.5 kg of a polymer having an isotactic triad fraction of 99.5%, an MFR of 3.0g/10min, a weight-average molecular weight by GPC of 251000, an Mw/Mn of 7.8 and an ME of 1.30 was obtained.
  • propylene polymers which are not only excellent in rigidity and heat resistance but also have much high-molecular weight components and favorable molding processability.

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  • Polymers & Plastics (AREA)
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DE2002619891 DE60219891T2 (de) 2002-05-31 2002-05-31 Propylenpolymer
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EP2177544A1 (fr) * 2007-08-06 2010-04-21 Japan Polypropylene Corporation Polymère de propylène, son procédé de fabrication, composition le contenant et son utilisation
US7799841B2 (en) 2006-08-25 2010-09-21 Borealis Technology Oy Polypropylene foam
US7914899B2 (en) 2006-07-10 2011-03-29 Borealis Technology Oy Electrical insulation film
US7915367B2 (en) 2006-12-28 2011-03-29 Borealis Technology Oy Process for the manufacture of branched polypropylene
US8142902B2 (en) 2006-08-25 2012-03-27 Borealis Technology Oy Extrusion coated substrate
US8247052B2 (en) 2006-09-25 2012-08-21 Borealis Technology Oy Coaxial cable
WO2013030188A1 (fr) * 2011-08-30 2013-03-07 Total Research & Technology Feluy Fibres et non tissés comprenant un copolymère aléatoire de propylène et procédé de production des fibres

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US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
EP2261292B1 (fr) 2002-10-15 2014-07-23 ExxonMobil Chemical Patents Inc. Compositions à base d'adhesifs polyolefiniques
US7563836B2 (en) * 2003-10-07 2009-07-21 Dow Global Technologies, Inc. Polypropylene composition for air quenched blown films
US20050170727A1 (en) * 2004-01-27 2005-08-04 Melik David H. Soft extensible nonwoven webs containing fibers with high melt flow rates
CN101248132A (zh) * 2005-08-22 2008-08-20 三井化学株式会社 丙烯类树脂组合物
EP1847555A1 (fr) 2006-04-18 2007-10-24 Borealis Technology Oy Polypropylène à ramifications multiples
EP2810883A1 (fr) * 2013-06-06 2014-12-10 Basell Poliolefine Italia S.r.l. Terpolymère à base de propylène pour contenants
EP2810884A1 (fr) * 2013-06-06 2014-12-10 Basell Poliolefine Italia S.r.l. Terpolymère à base de propylène pour contenants
JP6750239B2 (ja) * 2015-04-07 2020-09-02 日本ポリプロ株式会社 固体酸、オレフィン重合用触媒及びオレフィン重合体の製造方法
US10883197B2 (en) 2016-01-12 2021-01-05 Chevron Phillips Chemical Company Lp High melt flow polypropylene homopolymers for fiber applications

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US8142902B2 (en) 2006-08-25 2012-03-27 Borealis Technology Oy Extrusion coated substrate
US7799841B2 (en) 2006-08-25 2010-09-21 Borealis Technology Oy Polypropylene foam
US8247052B2 (en) 2006-09-25 2012-08-21 Borealis Technology Oy Coaxial cable
US7915367B2 (en) 2006-12-28 2011-03-29 Borealis Technology Oy Process for the manufacture of branched polypropylene
EP2177544A4 (fr) * 2007-08-06 2011-01-26 Japan Polypropylene Corp Polymère de propylène, son procédé de fabrication, composition le contenant et son utilisation
EP2177544A1 (fr) * 2007-08-06 2010-04-21 Japan Polypropylene Corporation Polymère de propylène, son procédé de fabrication, composition le contenant et son utilisation
US8080624B2 (en) 2007-08-06 2011-12-20 Japan Polypropylene Corporation Propylene-based polymer, production method therefor, composition using the same, and application thereof
WO2013030188A1 (fr) * 2011-08-30 2013-03-07 Total Research & Technology Feluy Fibres et non tissés comprenant un copolymère aléatoire de propylène et procédé de production des fibres
EA026322B1 (ru) * 2011-08-30 2017-03-31 Тотал Ресерч & Технолоджи Фелай Нетканые материалы, содержащие статистический сополимер пропилена

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